EP0457178A1 - Enveloppes tubulaires à base de cellulose, notamment enveloppes pour saucisses - Google Patents

Enveloppes tubulaires à base de cellulose, notamment enveloppes pour saucisses Download PDF

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Publication number
EP0457178A1
EP0457178A1 EP91107469A EP91107469A EP0457178A1 EP 0457178 A1 EP0457178 A1 EP 0457178A1 EP 91107469 A EP91107469 A EP 91107469A EP 91107469 A EP91107469 A EP 91107469A EP 0457178 A1 EP0457178 A1 EP 0457178A1
Authority
EP
European Patent Office
Prior art keywords
copolymer
casing
weight
group
cellulose
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP91107469A
Other languages
German (de)
English (en)
Other versions
EP0457178B1 (fr
Inventor
Klaus-Dieter Dr. Hammer
Manfred Dr. Siebrecht
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Hoechst AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Priority to DE9116861U priority Critical patent/DE9116861U1/de
Publication of EP0457178A1 publication Critical patent/EP0457178A1/fr
Application granted granted Critical
Publication of EP0457178B1 publication Critical patent/EP0457178B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A22—BUTCHERING; MEAT TREATMENT; PROCESSING POULTRY OR FISH
    • A22C—PROCESSING MEAT, POULTRY, OR FISH
    • A22C13/00—Sausage casings
    • A22C13/0013—Chemical composition of synthetic sausage casings
    • A—HUMAN NECESSITIES
    • A22—BUTCHERING; MEAT TREATMENT; PROCESSING POULTRY OR FISH
    • A22C—PROCESSING MEAT, POULTRY, OR FISH
    • A22C13/00—Sausage casings
    • A22C2013/004—Sausage casings with at least one layer of a gas, e.g. oxygen, water vapour, impermeable material
    • A—HUMAN NECESSITIES
    • A22—BUTCHERING; MEAT TREATMENT; PROCESSING POULTRY OR FISH
    • A22C—PROCESSING MEAT, POULTRY, OR FISH
    • A22C13/00—Sausage casings
    • A22C2013/0096—Sausage casings cellulosic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S206/00—Special receptacle or package
    • Y10S206/802—Shirred sausage casing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1324—Flexible food casing [e.g., sausage type, etc.]

Definitions

  • the invention relates to a tubular packaging casing, in particular sausage casing, based on cellulose, in particular fiber-reinforced cellulose, with a barrier layer against atmospheric oxygen and water vapor.
  • PVDC vinylidene chloride copolymer
  • Casings of this type are used because of their barrier layer on the inside as sausage casings for cooked and cooked sausages.
  • the polyacrylate dispersion is applied to the outside of the cellulose casing on the hose which is still in the gel state during its manufacture from viscose, i.e. even before drying.
  • This casing is permeable to water vapor and is intended as a sausage casing for dry sausage, dry sausage and raw sausage types. It is not suitable for cooked and scalded sausages.
  • Barrier layers based on PVDC have the advantage that the finished sausage loses practically no water during storage, and the sausage casing is still plump and wrinkle-free on the contents even after storage. Sausages of the liver sausage type, whose sausage meat discolors unsightly due to the action of atmospheric oxygen, remain unchanged, since the PVDC layer simultaneously forms a barrier to atmospheric oxygen and prevents atmospheric oxygen from penetrating into the sausage meat.
  • a fiber-reinforced cellulose casing with a 10 to 12 ⁇ m thick PVDC coating shows, for example, an extremely low water vapor permeability of 0.5 to 2 g / m2 24 h and an extremely low oxygen permeability of 2.5 to 4 cm3 / m2 24 h bar (measured in each case according to DIN 53 122 on 5 cm2 envelope surface).
  • the weight loss when stored in the cold room (7 ° C, 65% rh) is between 0.5 and 1.5% per week (with 60 mm caliber) .
  • the actual shell material consists of cellulose, namely cellulose hydrate, which is also referred to as regenerated cellulose or cellophane.
  • the packaging envelope consists of a seamless tube, but tubes with a longitudinal seam are also suitable, which are produced, for example, by folding a cellulose film in the axial direction and gluing the overlapping edges.
  • the packaging envelope is either unreinforced, but preferably fiber-reinforced.
  • the fiber-reinforced sausage casing which is usually referred to as fiber casing, is used particularly for large-caliber sausages.
  • the fiber-reinforced tubular packaging casing then shows the usual diameter of 30 to 180 mm for large sausage casings. It is reinforced with a tubular fiber web, which is provided on the inside and / or outside with cellulose.
  • the barrier layer of the invention can also be applied directly to the relatively rough surface of the fiber reinforcement without the barrier layer detaching from this base. It is therefore not necessary according to the invention that a cellulose layer is located between the barrier layer and the fiber reinforcement.
  • the fiber reinforcement usually consists of the usual long fiber papers based on consolidated nonwovens made from hemp fibers, but other textile fabrics are also suitable.
  • the cellulose tube to be coated is produced in the usual way, for example by the viscose process.
  • a tube or a fibrous web formed into a tube for example made of paper or hemp fibers, is coated on the inside and / or outside with an alkaline viscose solution through a ring nozzle and treated with an acidic precipitation liquid which causes the viscose to coagulate.
  • the viscose solution may contain the dye pigments required to form a white or colored shell.
  • the viscose is pressed directly into the coagulation bath in the form of a tube.
  • the possibly fiber-reinforced tube made of cellulose hydrate gel is passed through the usual washing baths and plasticizing baths.
  • the surface of the hose to be provided with the barrier layer optionally coated with an agent which forms an adhesion-promoting layer between the barrier layer and the cellulose layer or between the barrier layer and the fiber reinforcement.
  • This coating is carried out in the usual way, for example by soaking in a liquid bath, roller application or spraying.
  • the cationic resins customary for barrier layers made of PVDC are applied in still water-soluble form, which are crosslinked in the final drying process and converted into their water-insoluble form.
  • Suitable resin solutions are, in particular, aqueous epichlorohydrin-polyamine polyamide solutions which are commercially available. The concentration of these resin solutions is 0.8 to 5, in particular 1 to 3,% by weight.
  • the drying process takes place, in which the water content is usually reduced to values of 7 to 15%.
  • the resulting cellulose tube has a customary plasticizer content, preferably from 15 to 30% by weight, based on the weight of the casing, and is used in this state for coating with the copolymer of the invention.
  • the coating liquid for the bonding agent expediently contains the plasticizer for the cellulose, in particular monohydric or polyhydric alcohols, such as e.g. Glycerin and / or propanediol (propylene glycol), or mixtures thereof in the usual amount.
  • the plasticizer for the cellulose in particular monohydric or polyhydric alcohols, such as e.g. Glycerin and / or propanediol (propylene glycol), or mixtures thereof in the usual amount.
  • the packaging wrapper shows the barrier layer of the invention on its inner and / or outer surface.
  • a single coating ie on the inside or Outside of the case, sufficient.
  • the coating is only on the inside of the cellulose casing.
  • the cellulose material which is uncoated on the outside of the casing, can dry out and shrink after the sausage has been scalded, so that the sausage casing then fits tightly and wrinkle-free on the sausage meat.
  • the barrier layer according to the invention forms a closed, coherent film and has a weight per unit area that is sufficient to reduce the water vapor permeability of the cellulose casing to a value of less than or equal to 50 g / m 2 for 24 hours.
  • the coating should reduce the oxygen permeability of the casing to values equal to / less than 12 cm3 / m2 24 h bar (measured in accordance with DIN 53 122 on 5 cm2 casing surface with a water content of the casing of 8 to 10% by weight and a glycerol content of 20% by weight). These values are achieved by a minimum basis weight of 12 g of the barrier layer per m2 cover surface, the basis weight of the gas-tight coating being present on the inside and / or outside of the cover.
  • a minimum of 14 to 15 g / m2 is used for the basis weight of the coating in order to achieve even lower permeability values.
  • a coating thickness corresponding to a basis weight of 18 to 25, in particular 20 to 30 g / m2 optimal properties are achieved on the inside or outside of the casing.
  • the water vapor permeability can be reduced to about 5 g / m2 24 h and the oxygen permeability to about 5 cm3 / m2 24 h bar.
  • the copolymer of the barrier layer is built up from vinyl monomers and is largely tack-free, which is achieved by setting the highest possible average molecular weight of the copolymer. It is known that high molecular weights can be achieved by particularly slow polymerization.
  • the mixture of the compounds to be polymerized is cooled sufficiently to extend the reaction time.
  • the value for the relative viscosity of the copolymer in the organic solvent must be determined. In dimethylformamide (DMF) this value should be for a 1 wt. % copolymer solution amount to at least 2.6, in particular at least 3.0.
  • the flow time is determined with a capillary, diameter 0.5 mm (KPG viscometer according to Ostwald).
  • the plastic coating essential to the invention is provided on the inside, it expediently additionally contains a wax, for example a vegetable wax such as candelilla, carnauba or montan wax, an animal wax such as beeswax, a mineral wax such as polyolefin wax, which consists of n- and iso-paraffins , or a synthetic wax, e.g. based on oxazoline.
  • a particularly suitable wax is chemically modified montan wax (KPS type, manufacturer Hoechst). These waxes are described as an additive to hydrophilic copolymers in EP-A-0 100 056.
  • particulate solid particles are particularly suitable which are sufficiently heat-stable so that they do not melt when the copolymer dispersion applied to the shell dries.
  • lubricants include pigments based on SiO2, CaCO3 and aluminum silicate with an average particle diameter of less than 4, in particular less than 2 ⁇ m.
  • the barrier layer consists of one or more copolymers. These copolymers of the barrier layer consist of at least two, preferably two to four, vinyl monomers, which preferably have hydrophilic groups and consist of the comonomers mentioned in claim 1. In particular embodiments, the vinyl monomers mentioned in claim 2 and / or 3 are additionally present in the copolymer.
  • the additional up to 45% by weight of vinyl monomers present in the copolymer are (meth) acrylic acid and (meth) acrylonitrile. In general, however, the proportion of these comonomers is relatively low.
  • (Meth) acrylic acid is usually present in the copolymer in an amount of 0.1 to 20 and (meth) acrylonitrile in an amount of 0.1 to 35% by weight.
  • the further vinyl monomers mentioned in claim 3 are present in the copolymer.
  • the following monomers are involved: vinyl acetal, butadiene, isoprene, styrene, crotonic acid (ester), itaconic acid (ester) and maleic acid (ester), the alcohol component of the esters having 1 to 10, in particular 1 to 5, carbon atoms.
  • the proportion of these further vinyl monomers is a maximum of 45% by weight.
  • the proportion of all other vinyl monomers (claims 2 and 3) is in any case less than 50% by weight, so that the comonomers of claim 1 always predominate in the copolymer.
  • the copolymer consists of one, two or three (meth) acrylic acid esters, which together comprise at least 60, in particular at least 85,% by weight of the copolymer.
  • the cellulose tube is coated with an aqueous solution or dispersion of the copolymer and the solvent or dispersion medium is removed by the action of heat.
  • the hose still contains large amounts of water, its surface temperature hardly rises above 100 ° C.
  • the copolymer applied which is in the form of small spheres, is sintered or melted at elevated temperature, in particular at 130 to 170 ° C., in order to produce a closed film.
  • the concentration of the coating liquid is generally 15 to 40% by weight.
  • the coating liquid may contain conventional additives such as dispersing aids, dyes, emulsifiers and lubricants.
  • the barrier layer is also to contain a wax
  • an additional 0.5 to 3% by weight (based on the copolymer) of wax is added to the coating liquid.
  • the coating liquid optionally also contains 0.5 to 2% by weight (based on the copolymer) of heat-stable, in particular inorganic, pigment as a lubricant.
  • the coating liquid is applied using conventional devices as are known for the production of inner and outer coatings of cellulose tubes. Also removing the coating liquid and the copolymer is melted into a dense, coherent plastic film using conventional drying devices.
  • the tubular casing is particularly suitable as a sausage casing for cooked and scalded sausages, for which PVDC barrier layers have previously been provided.
  • the 60 mm caliber sausages with a length of 50 cm show a weight loss of 1.5 to a maximum of 4% per week due to water release.
  • the good barrier properties of PVDC barrier layers are not quite achieved by the barrier layer of the invention, the properties achieved are already completely sufficient for many types of sausage.
  • the casings according to the invention represent an advantageous alternative.
  • tubular casing is laid flat and stored in roll form, processed into sections tied on one side or gathered into caterpillars.
  • the coating is sufficiently firm, flexible, stretchable for the processing steps and does not become brittle when stored.
  • the casing has the usual plasticizer and water content for cellulose-based sausage casings.
  • the tube is guided vertically upwards so that excess dispersion can run off, passed through a pair of metering rollers, as shown in EP-A-0 037 023, then dried in the inflated state and then heated to about 160 ° C., the copolymer particles sinter together into a closed coating.
  • the casings After drying, the casings show an inner barrier layer of 18 to 25 g / m2.
  • the coating weight is determined by peeling with DMF.
  • the tubular casing is moistened and gathered into caterpillars. After the caterpillars had been stored for one week in the pressed state under tropical conditions (38 ° C, 86% r.h.), the shirred folds are undamaged, i.e. still sufficiently tight.
  • the copolymer of composition (a) produces an inner coating which leads to a particularly good peelability of the casing from the sausage mass.
  • the copolymers By selecting the copolymers, the desired adhesion and peelability of the casing can also be set.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • Laminated Bodies (AREA)
  • Processing Of Meat And Fish (AREA)
  • Wrappers (AREA)
  • Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
  • Packages (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP91107469A 1990-05-16 1991-05-08 Enveloppes tubulaires à base de cellulose, notamment enveloppes pour saucisses Expired - Lifetime EP0457178B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE9116861U DE9116861U1 (de) 1990-05-16 1991-05-08 Schlauchförmige Verpackungshülle, insbesondere Wursthülle, auf Basis von Cellulose

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4015659A DE4015659A1 (de) 1990-05-16 1990-05-16 Schlauchfoermige verpackungshuelle, insbesondere wursthuelle, auf basis von cellulose
DE4015659 1990-05-16

Publications (2)

Publication Number Publication Date
EP0457178A1 true EP0457178A1 (fr) 1991-11-21
EP0457178B1 EP0457178B1 (fr) 1994-03-09

Family

ID=6406497

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91107469A Expired - Lifetime EP0457178B1 (fr) 1990-05-16 1991-05-08 Enveloppes tubulaires à base de cellulose, notamment enveloppes pour saucisses

Country Status (8)

Country Link
US (1) US5316809A (fr)
EP (1) EP0457178B1 (fr)
AT (1) ATE102439T1 (fr)
DE (3) DE4015659A1 (fr)
DK (1) DK0457178T3 (fr)
ES (1) ES2050479T3 (fr)
FI (1) FI99078C (fr)
HU (1) HU215568B (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0557819A1 (fr) * 1992-02-25 1993-09-01 Wolff Walsrode Aktiengesellschaft Enveloppe tubulaire, renfermant des revêtements exempts de chlore organique, imperméables à l'oxygène et à la vapeur d'eau, son procédé de fabrication et son application
WO1996036653A3 (fr) * 1995-05-18 1997-01-09 Stoess & Co Gelatine Materiau d'arret resistant a l'eau
US6627282B2 (en) 1997-09-26 2003-09-30 Kalle Nalo Gmbh & Co. Kg Internally coated food casings based on regenerated cellulose
WO2003101209A1 (fr) 2002-05-31 2003-12-11 Casetech Gmbh & Co. Kg Boyau a saucisse permeable a la fumee a base d'hydrate de cellulose pourvu de couches d'arret autoadhesives sur sa surface exterieure et procede de fabrication dudit boyau
WO1993019121A3 (fr) * 1992-03-11 2004-04-29 Buertex Buerker & Co Gmbh Feuille putrescible renforcee par fibres

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19912052A1 (de) 1999-03-18 2000-09-21 Kalle Nalo Gmbh & Co Kg Beschichtete, faserverstärkte Hülle auf Basis von Cellulosehydrat für geräucherte Leberwurst
CN100506398C (zh) * 2003-07-30 2009-07-01 海南赛诺实业有限公司 热收缩型涂布薄膜的生产方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0001545A1 (fr) * 1977-08-05 1979-05-02 Hoechst Aktiengesellschaft Enveloppe tubulaire à base d'hydrate de cellulose, notamment enveloppe d'emballage, p.e. enveloppe pour saucisses et procédé pour sa fabrication
FR2441558A1 (fr) * 1978-11-18 1980-06-13 Becker & Co Naturinwerk Gaine pour l'emballage et l'enveloppement de produits alimentaires, en particulier de saucisses et de fromages
US4463778A (en) * 1978-03-17 1984-08-07 Teepak, Inc. Sausage casing formed from regenerated cellulose with an internal vinyl acetate coating
EP0286025A1 (fr) * 1987-04-06 1988-10-12 Hoechst Aktiengesellschaft Objets façonnés durablement plastifiés à base de cellulose

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2512995C3 (de) * 1975-03-24 1979-11-29 Hoechst Ag, 6000 Frankfurt Folienschlauch, insbesondere Verpackungshülle
DE3012250C2 (de) * 1980-03-28 1982-10-14 Hoechst Ag, 6000 Frankfurt Verfahren zur Herstellung eines Schlauchs mit einem Filmüberzug aus Kunststoff auf der Innenseite, seine Verwendung, sowie Vorrichtung zur Durchführung des Verfahrens
DE3227920A1 (de) * 1982-07-27 1984-02-02 Hoechst Ag, 6230 Frankfurt Cellulaseresistente lebensmittelhuelle
DE3343635A1 (de) * 1983-12-02 1985-06-13 Hoechst Ag, 6230 Frankfurt Folie aus faserverstaerkter regenerierter cellulose mit gasundurchlaessiger schicht zur herstellung von schlauchhuellen
DE3538702A1 (de) * 1985-10-31 1987-05-07 Hoechst Ag Sauerstoff- und wasserdampfundurchlaessige folie zur herstellung geraffter schlauchhuellen, insbesondere wursthuellen

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0001545A1 (fr) * 1977-08-05 1979-05-02 Hoechst Aktiengesellschaft Enveloppe tubulaire à base d'hydrate de cellulose, notamment enveloppe d'emballage, p.e. enveloppe pour saucisses et procédé pour sa fabrication
US4463778A (en) * 1978-03-17 1984-08-07 Teepak, Inc. Sausage casing formed from regenerated cellulose with an internal vinyl acetate coating
FR2441558A1 (fr) * 1978-11-18 1980-06-13 Becker & Co Naturinwerk Gaine pour l'emballage et l'enveloppement de produits alimentaires, en particulier de saucisses et de fromages
EP0286025A1 (fr) * 1987-04-06 1988-10-12 Hoechst Aktiengesellschaft Objets façonnés durablement plastifiés à base de cellulose

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0557819A1 (fr) * 1992-02-25 1993-09-01 Wolff Walsrode Aktiengesellschaft Enveloppe tubulaire, renfermant des revêtements exempts de chlore organique, imperméables à l'oxygène et à la vapeur d'eau, son procédé de fabrication et son application
WO1993019121A3 (fr) * 1992-03-11 2004-04-29 Buertex Buerker & Co Gmbh Feuille putrescible renforcee par fibres
WO1996036653A3 (fr) * 1995-05-18 1997-01-09 Stoess & Co Gelatine Materiau d'arret resistant a l'eau
US6627282B2 (en) 1997-09-26 2003-09-30 Kalle Nalo Gmbh & Co. Kg Internally coated food casings based on regenerated cellulose
WO2003101209A1 (fr) 2002-05-31 2003-12-11 Casetech Gmbh & Co. Kg Boyau a saucisse permeable a la fumee a base d'hydrate de cellulose pourvu de couches d'arret autoadhesives sur sa surface exterieure et procede de fabrication dudit boyau

Also Published As

Publication number Publication date
ES2050479T3 (es) 1994-05-16
EP0457178B1 (fr) 1994-03-09
DE9116861U1 (de) 1994-04-14
DK0457178T3 (da) 1994-05-02
ATE102439T1 (de) 1994-03-15
US5316809A (en) 1994-05-31
FI912342A0 (fi) 1991-05-14
HU911631D0 (en) 1991-11-28
FI99078B (fi) 1997-06-30
HU215568B (hu) 1999-01-28
FI912342L (fi) 1991-11-17
DE59101135D1 (de) 1994-04-14
FI99078C (fi) 1997-10-10
HUT60453A (en) 1992-09-28
DE4015659A1 (de) 1991-11-21

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